在双磺酸基官能化Brφnsted酸性离子液体/[bmim]Br中均相合成山梨醇类成核透明剂  

Synthesis of Sorbitol Nucleating Agent in Double SO_3 H-Functionalized Brφnsted Acidic Ionic Liquids/[bmim]Br Under Homogeneous Conditions

作　　者：李心忠[1] 陈亚英[1] 林棋[1] 

机构地区：[1]闽江学院化学与化学工程系,福建福州350108

出　　处：《精细化工》2013年第9期1068-1072,共5页Fine Chemicals

基　　金：福建省教育厅科研项目(JK2010044);福建省科技厅重大项目(2011H06021);福州市科技项目(2012-G-138);福建省大学生创新实验(MJU201241039)~~

摘　　要：以脂肪多胺四甲基乙二胺、五甲基二乙烯三胺、1,3-丙烷磺内酯为起始原料,经季铵化、酸化两步反应,合成了两种阳离子结构中具有双磺酸基官能团的Bronsted酸功能化离子液体二（3-磺酸基）丁基四甲基乙二铵硫酸氢根盐、二（3-磺酸基）丁基五甲基乙二烯三铵硫酸氢根盐,离子液体的结构经红外光谱、核磁共振氢谱得到确认,以4-硝基苯胺为指示剂测定离子液体的Hammett酸函数,两种离子液体酸强度均高于硫酸.以合成的离子液体与1-丁基-3-甲基咪唑溴化物构成的二元离子液体体系为反应体系,应用于山梨醇与苯甲醛、对甲基苯甲醛、3,4-二甲基苯甲醛的缩合反应中,结果表明,当离子液体的摩尔分数为15％（以山梨醇计）,n（山梨醇）∶n（醛）=1∶2.05,于70℃反应4h时,反应即可在无溶剂均相反应条件下顺利完成,体系中加入水,目标化合物即可析出,分离产率77.6％ ～ 84.8％,产物熔距≤5℃,二元离子液体经旋蒸除水,乙醚洗涤、真空干燥后可循环使用,循环使用5次催化活性基本保持不变.Two double SO3H-functionlized Bronsted acidic ionic liquids BAILs-1 and BAILs-2 were synthesized by using commercially available aliphatic polyamine tetramethylethylene diarnaine, pentamethyldiethylenetriamine and 1,3-propanesultone as the source chemicals via a two-step reaction of quaternarization and acidification. Their structures were confirmed by FTIR and 1HNMR, and their Hammett acidic functions were determinated by UV spectrum using 4-nitroanilins as indicator. The two ionic liquids showed higher acidity than H2SO4. BAILs-1 and BAILs-2, which acted as catalyst and medium together with [ bmim ] Br for the synthesis of sorbitol transparent nucleating agent were studied, and the results indicate that the reaction could be carried out smoothly under homogeneous reaction conditions. The optimized conditions as follows：the molar fraction of BAILs-1 or 2 was 15% （based on sorbitol） ,the molar ratio of sorbitol/aldehyde was 1：2.05, and the reaction was completed at 70 ℃ for four hours. When water was added into the system, the target product could be isolated in yields of 77.6% - 84. 8% with melting range ≤5 ℃. The ionic liquids could be recovered after removal of water in vacuum and being washed with ether, and could be reused for five times without significant loss in their catalytic activity.

关 键 词：BRΦNSTED酸 离子液体 成核透明剂 均相合成 山梨醇 精细化工中间体 

分 类 号：TQ223.166[化学工程—有机化工] TQ426.7